The influence of anolyte composition and temperature on the anode dissolution kinetics of pure iron and subsequent ferrate(VI) production was studied by means of potentiodynamic voltammetry and electrochemical impedance spectroscopy. The results obtained were verified by batch electrolyses. Pure NaOH, KOH, and mixtures thereof were used as an anolyte. The motivation for this study is to understand in more detail the electrolysis process at which ferrate(VI) is electrochemically produced in situ in the solid form which is more suitable for practical utilization. A significant impact of the anolyte composition on the system behavior was indicated. It is related to the solubility of the anode dissolution products in the anolyte. It was concluded that the fast reaction kinetics in the transpassive potential region is connected with a deterioration of the ferrate(VI) synthesis efficiency. This is explained by the kinetic enhancement corresponding to the intensification of oxygen evolution as a parasitic reaction.